CN114275759A - Hierarchical porous carbon material and preparation method and application thereof - Google Patents
Hierarchical porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of organic porous materials, in particular to a hierarchical porous carbon material and a preparation method and application thereof. The surface modification is carried out on the SiO2 nanosphere by adopting trichloro (4-chloromethylphenyl) silane to obtain the R-SiO2 template agent with the surface containing benzyl chloride chemical functional groups. And then carrying out in-situ hypercrosslinking reaction on the surface of R-SiO2 by taking DCX-as a self-crosslinking functional monomer to obtain R-SiO2@ DCX, removing the-SiO 2 nanosphere template of R-SiO2@ DCX to prepare HPP, and finally carrying out high-temperature carbonization treatment to obtain the HPC. The invention prepares the SiO2 reactive template agent containing benzyl, prepares the hierarchical pore material with micropore-mesopore-macropore by inducing in-situ hypercrosslinking reaction by the reactive template agent, and the prepared hierarchical pore carbon material has stable sample structure and better adsorption performance and capacitance performance.
Description
Technical Field
The invention relates to the field of organic porous materials, in particular to a hierarchical porous carbon material and a preparation method and application thereof.
Background
The hierarchical porous material has a high specific surface area, high porosity, good permeability and a highly ordered pore structure, and the hierarchical porous material having micro-pores, meso-pores and macro-pores is widely applied in the related fields of adsorption, energy storage, super-capacitance and the like due to the excellent performances of diversified pore structures, high specific surface area, good chemical stability and the like, and gradually becomes the focus of attention of researchers.
The preparation method of the hierarchical porous carbon material can be divided into a hard template method and a soft template method according to different synthesis modes. And (3) synthesizing a template with a preset structure for the hard template, filling, crosslinking and carbonizing, and washing off the template to prepare the hierarchical porous carbon material. The soft template method is to remove the precursor at high temperature by the self-assembly reaction of the precursor and the polymer and utilizing the difference of chemical properties between the precursor and the polymer to form a pore structure, and the polymer becomes a carbon skeleton. Hierarchical pore polymers used as carbon precursors in the carbonization process are porous materials with good pore structures.
However, the conventional hard template method still has some disadvantages. When the hierarchical pore material is prepared by using the template agent, the precursor is required to be used in the traditional crosslinking reaction, the precursor is combined with the macromolecule through covalent chemical bonds, so that the preparation process is slightly complicated, and the grafting degree depends on the chemical bond combination degree. Although cross-linking bridges can be generated among polymers under the catalysis condition, due to the difference of chemical structures among the polymers, a heterogeneous interface is easily generated in the process of synthesizing a template, so that the prepared super-cross-linked polymer is easy to agglomerate, poor in dispersity and the like, and the unstable cross-linked structure can cause skeleton collapse in the subsequent carbonization process, damage the internal hole structure of the material and influence further performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a hierarchical porous carbon material, wherein a prepared hierarchical porous carbon material sample has a stable structure and has better adsorption performance and capacitive performance.
The invention is realized by the following steps:
the invention firstly provides a preparation method of a hierarchical porous carbon material, which comprises the following steps:
(1)R-SiO2preparation of
Mixing SiO20.5g of dry tetrahydrofuran THF (20 ml) and 1.5g of trichloro [4- (chloromethyl) phenyl ] ethyl acetate are added]A mixture of silanes; in N2In the atmosphere, 5.0ml of dry THF and 1.2ml of triethylamine are uniformly mixed, added into the system at a constant speed for reaction for 8 hours, and then reacted in the air for 18 hours; after the reaction was complete, the product was washed with EtOH and THF at least 3 times and dried;
(2)R-SiO2preparation of @ DCX
In N2In the atmosphere, adding R-SiO20.5g of FeCl was uniformly dispersed in 10ml of dichloroethane DCE and dried3-1.1-2.0g of the mixture is quickly added into the mixture and evenly stirred, 1.5g of p-dichlorobenzene DCX is dissolved in 10ml of dichloroethane DCE, the mixed solution is added into a three-neck flask when the reaction system is heated to 70-90 ℃, and the mixed solution is dropwise added for 6 hours and kept to react for 18 hours; washing the product with deionized water, washing with deionized water and methanol until no color, washing with diethyl ether for 3 times, and drying.
(3) Preparation of HPP and HPC
Preparing 10% HF, mixing R-SiO2Adding @ DCX into the mixture, keeping magnetic stirring at 500rpm for 24h, washing off residual HF solution, drying at 60 deg.C for 12h to obtain hierarchical porous polymer HPP, placing HPP, N in a tube furnace2The purging speed is 80-100ml/min, the carbonization temperature is 700-.
Preferably:
catalyst FeCl in step (2)3The amount used was 1.6g and the crosslinking temperature was 80 ℃.
The carbonization temperature in the step (3) is 1000 ℃, the carbonization temperature rise rate is 5 ℃/min, and the carbonization time is 3 h.
The invention also provides the hierarchical porous carbon material prepared by the preparation method.
The invention also provides application of the hierarchical porous carbon material in preparation of dye adsorbents or electrode materials.
When the hierarchical porous carbon material is used as a dye adsorbent, taking 10mL of MB solution with the concentration of 50mg/L as a standard solution, respectively adding HPC under different HPC dosage, different pH values and adsorption sampling time, and stirring until adsorption balance; when the adding amount is 6mg, the adsorption rate reaches the highest value; HPC reached maximum adsorption performance at pH 9.39; when the adsorption sampling time is 60min, the adsorption rate reaches the highest value; the maximum adsorption rate was reached when the adsorption temperature was 40 ℃.
The invention has the following advantages: the invention takes SiO2 nanospheres with benzyl chloride on the surface as a reactive template agent and 1, 4-Dichlorobenzyl (DCX) as a self-crosslinking functional monomer to prepare the hierarchical pore material with micropores, mesopores and macropores. On one hand, DCX can react with benzyl chloride on the surface of SiO2 in situ to form a covalent bond, which is beneficial to high monodispersion of a template agent and uniform coating of covalent organic polymers on the surface; on the other hand, DCX molecules can be subjected to self-crosslinking, so that the additional addition of a crosslinking agent is avoided, and the preparation process is simplified; moreover, the covalent organic framework has a super-crosslinking chemical structure, so that stable inheritance in the hierarchical pore structure preparation process can be ensured. Meanwhile, the preparation conditions of the hierarchical porous polymer HPP and the carbon material HPC thereof are optimized, and the adsorption performance and electrochemical characteristics of the hierarchical porous polymer HPP and the carbon material HPC are researched.
The method comprises the following specific steps:
(1) HPP with micropores, mesopores and macropores is successfully prepared by inducing in-situ hypercrosslinking reaction through a reactive template agent. The pore structure of HPP can be regulated and controlled by changing the concentration of the catalyst, the crosslinking temperature and the crosslinking time in the reaction process, and when the dosage of the catalyst is 1.6g, the crosslinking temperature is 80 ℃, and the crosslinking time is 24 hours, the specific surface area of the HPP reaches the maximum value of 899m2·g-1。
(2) The carbon material formed by carbonizing HPP at high temperature inherits the hierarchical pore structure of HPP, and the hierarchical pore carbon material (HPC) is obtained. The carbonization temperature, carbonization time, and carbonization heat-up rate significantly affect the HPC pore structure, thereby altering HPC pore size distribution and specific surface area. When the carbonization temperature is 1000 ℃, carbonizingThe time is 3h, the carbonization temperature rise rate is 5 ℃/min, the HPC specific surface area reaches the maximum value 2388m2· g-1。
(3) The dye molecules in the solution can be effectively adsorbed by using HPC as an adsorbent. The dosage, pH value, adsorption temperature and adsorption time of the adsorbent all affect the adsorption process, the adsorption condition is optimized, and the adsorption rate can reach more than 95%; the adsorption process conforms to a pseudo-second-order kinetic model and a particle internal diffusion model, and shows that the adsorption reaction simultaneously comprises chemical adsorption and micropore internal adsorption.
(4) The electrode material of the zinc ion hybrid supercapacitor is prepared by HPC. After 100 times of circulation, the circulation discharge capacity is stabilized at 60mAh g-1About when the current density is 0.1A · g-1The capacitance is increased along with the increase of the cycle number, and the maximum capacitance can reach 35mAh g-1After 150 cycles, the reversible capacity can reach 40 mAh.g-1. The charging and discharging curves and the impedance curves of the first three circles show the stability of the electrode material.
Drawings
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
FIG. 1 is a scanning electron micrograph of the reactants; wherein (a) R-SiO2@ DCX nanospheres; (b) HPP; (c) SiO22@DCX。
FIG. 2 is-R-SiO2@ DCX infrared spectrogram.
Figure 3 is a plot of (a) nitrogen adsorption-desorption isotherms and (b) pore size distributions for HPC at various catalyst concentrations.
FIG. 4 is a scanning electron microscope image of different hypercrosslinking temperatures HPP; wherein (a) is 30 ℃; - (b)50 ℃; - (c)70 ℃; - (d)80 ℃; - (e)90 ℃.
FIG. 5 is a thermogravimetric analysis curve of HPP before acid wash at different hypercrosslinking temperatures.
FIG. 6 is a graph showing the effect of HPC dosage on its adsorption of methylene blue; wherein (a) the adsorption rate; (b) balancing the adsorption capacity.
Figure 7 is the effect of pH on HPC adsorption of methylene blue solution.
FIG. 8 is a graph of the effect of adsorption time on HPC adsorption of methylene blue; wherein (a) the adsorption rate; (b) balancing the adsorption capacity.
FIG. 9 is a graph of the effect of temperature on HPC adsorption of methylene blue; wherein (a) the adsorption rate; (b) balancing the adsorption amount.
Fig. 10 shows (a) a cycle characteristic curve and (b) a rate characteristic curve of the HPC carbon electrode material.
FIG. 11 shows (a) a charge/discharge curve and (b) an impedance performance curve of the HPC carbon electrode material.
Detailed Description
Example 1
1 sample preparation
1.1-SiO2Preparation of
According to
The solution A is EtOH/NH3·H2O/H2112.5ml/8.4ml/104.5ml of O, 202.5ml/22.4ml of EtOH/TEOS of B solution. First, solution A was magnetically stirred in a three-necked flask at 1000rpm, and then the rotation speed was decreased to 250rpm, at which time solution B was rapidly added, and the reaction was continued for 3.5 hours. After centrifugation, the product was washed 3 times with absolute ethanol and dried under vacuum at 100 ℃ for 24 h.
1.2R-SiO2Preparation of
Mixing the above SiO2(0.5g) 20ml of dry Tetrahydrofuran (THF) and 1.5g of trichloro [4- (chloromethyl) phenyl ] are added]Silane mixture while maintaining magnetic stirring in a three-necked flask. In N2In the atmosphere, 5.0ml of dry THF and 1.2ml of triethylamine are uniformly mixed, added into the system at a constant speed and reacted for 8 hours, and then reacted for 18 hours in the air. After completion of the reaction, the product was washed at least 3 times with EtOH and THF and dried under vacuum at 60 ℃ for 24 h.
1.3-R-SiO2Preparation of @ DCX
In N2In the atmosphere, adding R-SiO2(0.5g) after homogeneously dispersing in 10ml of Dichloroethane (DCE), FeCl was dried3(catalyst, 1.6g) was quickly added thereto and stirred uniformly. 1.5g of p-Dichlorobenzene (DCX) was dissolved in 10ml of Dichloroethane (DCE), and when the reaction system was raised to 80 ℃, the mixed solution was added dropwise to a three-necked flask for 6 hours while maintaining the reactionAnd the time is 18 hours. The product is washed by deionized water, washed by deionized water and methanol until colorless, washed by diethyl ether for 3 times, and dried under vacuum for 24 hours at 60 ℃.
1.4 preparation of HPP and HPC
Preparing proper amount of 10% HF, and mixing R-SiO2@ DCX was added to the mixture while maintaining magnetic stirring at 500rpm for 24h, and the residual HF solution was washed off and dried at 60 ℃ for 12h to give Hierarchical Pore Polymer (HPP). Placing HPP, N in a tube furnace2And (4) carbonizing for 3h at the temperature of 900 ℃ at the blowing rate of 80-100ml/min to obtain the hierarchical porous carbon material (HPC).
2 characterization of the materials
2.1 scanning Electron microscopy analysis (SEM)
The microscopic morphological structure of the sample was observed by Scanning Electron Microscopy (SEM) of model S8010 from Hitachi, japan. Coating a trace amount of dried powdery sample on conductive adhesive, spraying gold for 80s, and then sending into an instrument for observation, wherein the scanning acceleration voltage is 5-10KV, and the acceleration current is 10 muA.
2.2 Fourier Infrared Spectroscopy test (FT-IR)
The absorption spectrum of the sample in the standard mid-infrared region was determined using a Fourier transform infrared spectrometer model TENSOR-27 from Bruker, Germany. A small amount of powdery dry sample is taken for testing, and the scanning range of the instrument is 4500--1Resolution of 1.0cm-1。
2.3 thermogravimetric analysis (TGA)
The weight change of the material over a range of temperatures was measured using a SDT (TGA) thermogravimetric analyzer from Discovery, Inc. of USA. About 30mg of the sample was taken into a ceramic crucible, and the weight measurement was started after the weight was balanced. N is a radical of2The flow rate is 50ml/min, the equilibrium flow rate is 50ml/min, the heating rate is 10 ℃/min, and the target temperature is 800 ℃.
2.4-N2Adsorption-desorption characterization (ASAP)
The pore structure and specific surface area were determined using a fully automated physical chemical adsorption apparatus model ASAP2460 from micromeritics, usa. About 50mg of the sample is weighed out and degassed at a certain temperature for 3h (HPP: 120 ℃, HPC: 250 ℃). All samples are inN at 77K2Adsorption-desorption with minimum air inflow of 8-cm-3·g-1The delay balance time was 10 s. At a relative pressure P/P0The pore volume and the specific surface area were obtained from the nitrogen adsorption amount at 0.99, and the specific surface area of the sample was calculated according to the BET theory, and the adsorption-desorption isotherm curve and the pore size distribution of the sample were analyzed using the Density Functional Theory (DFT) using a slit pore model.
2.5 evaluation of adsorption Properties
And placing the sample to be tested in a quartz cuvette for quantitative test. Methylene blue is known as methylene blue hereinafter abbreviated as MB and has the chemical formula C16H18ClN3S·3H2O, molecular weight 320 g-moL1The molecular size is 1.43nm × 0.61nm × 0.40 nm. Methylene blue, a typical substance in dye wastewater, is commonly used as a representative model for dye adsorption experiments.
(1) Preparing standard liquid and calculating standard curve
Accurately weighing 50mg of methylene blue, placing the methylene blue into a 500mL beaker, adding a small amount of deionized water, stirring until the methylene blue is completely dissolved, transferring the methylene blue into a 1000mL volumetric flask in batches, metering the volume by using the deionized water, and uniformly shaking up and down to prepare a methylene blue standard solution with the concentration of 50 mg/L. The maximum absorption wavelength of the methylene blue standard solution was 664nm as measured by a UV2550 UV-spectrophotometer, and it was set as an absorbance baseline for measurement.
The prepared standard solution is diluted to 2.0mg/L, 4.0mg/L, 6.0mg/L, 8.0mg/L and 10.0mg/L respectively, and the corresponding absorbance values are measured. The ordinate is absorbance, the abscissa is concentration, through linear fitting, calculate the standard curve of the methylene blue standard solution, can obtain the standard curve equation as the formula, wherein the linear correlation coefficient R2Has a value of 0.99709.
Y＝0.18631x+0.03543 (21)
(2) Adsorption experiments
Putting a certain amount of methylene blue solution into a conical flask, adding a proper amount of HPC sample, adding a plug, magnetically stirring at room temperature, sucking out a proper amount of supernatant at intervals, removing impurities by using a filter membrane, putting the solution to be tested into a cuvette for absorption spectrum test, wherein the related calculation formula is as follows:
adsorption rate:
wherein w is the adsorption rate of the MB solution, and the unit is%; c0Initial mass concentration of MB solution, mg.L in unit1；CeThe MB solution concentration in mg. L at the time of adsorption equilibrium1(ii) a And m is the mass of the added HPC and is g.
Amount of adsorption at a certain time:
wherein q istIs the adsorption amount of MB solution at time t, in mg. L1；CtIs the adsorption amount of MB solution at time t, in mg. L1(ii) a V is the total volume of MB solution in L.
Adsorption amount at equilibrium:
wherein, CeThe MB solution concentration in mg. L at the time of adsorption equilibrium1；
2.6 evaluation of electrochemical Properties
(1) Preparing a zinc ion mixed super-capacitor electrode plate:
the prepared HPC sample, the conductive agent Super-P and the prepared 3.5% PVDF solution are sequentially placed on a mortar according to the mass ratio of 8:1:1, mixed and ground uniformly, a proper amount of N-methyl-2 pyrrolidone is dripped to prepare slurry, then the slurry is dispersed and coated on a stainless steel foil, and the stainless steel foil is placed in an oven at 70 ℃ and dried overnight. A circular electrode sheet with a radius of 6mm was then punched out using a punch.
(2) Assembly of zinc ion hybrid super capacitor
The zinc cathode and the fiber paper diaphragm are respectively cut into round pieces with the diameters of 12mm and 19mm for later use, and the electrolyte is 2M zinc sulfate aqueous solution. Assembling the positive electrode shell, the spring piece, the gasket, the positive electrode, the diaphragm, the zinc negative electrode and the negative electrode shell in sequence, adding 80 mu L of electrolyte, packaging into a CR2025 button cell by a button cell packaging machine, and standing all the supercapacitors for 30min before carrying out electrochemical test. As shown in the figure.
(3) Electrochemical test method:
the specific capacity and rate capability of the mass were tested using the novalway BTS battery test system. The test voltage range is 0.21.8-V, and the current density is 0.1 A.g-1The number of cycles was 100.
(4) The specific capacity of the zinc ion hybrid supercapacitor is calculated in the following way:
wherein Q is the specific capacity of the zinc ion mixed super capacitor in mA.h.g-1(ii) a I is a constant current, -in mA; t is the test time in units of h; m is the mass of the active substance in g.
3 results and analysis
3.1-R-SiO2@ DCX characterization
The SEM picture of FIG. 1(a) clearly shows that R-SiO2The surface of the @ DCX nanosphere presents a rough and uneven wrapping layer. As can be seen from FIG. 1(b), after the silica template is removed, R-SiO2The internal cavity of the @ DCX nanosphere retains the complete spherical structure. Obviously, the coating with rough surface is R-SiO2The polymer shell layer is used as a template and formed by the in-situ hypercrosslinking reaction of DCX serving as a monomer, which further proves that the DCX serving as a functional monomer can form a covalent bond by the in-situ hypercrosslinking reaction with benzyl chloride on the surface of the template agent, enhances the interaction force of a polymer precursor and the template agent, is beneficial to the high monodispersion of the template agent and the uniform coating of the surface of the template agent on the polymer, and forms a polymer with uniform sizeTemplate holes and a polymer backbone. According to FIG. 1(c), unmodified SiO is used2Polymer SiO formed by carrying out hypercrosslinking reaction2@ DCX has a flat surface and is in an agglomerated shape, which indicates that the R-SiO is not modified2The hypercrosslinking reaction cannot be performed using DCX.
Furthermore, R-SiO2The @ DCX nanospheres mutually keep good dispersibility without obvious agglomeration, because the nanospheres are wrapped from the outermost layer by Friedel-crafts reaction, and under the action of a catalyst, the groups of the monomers react at the contact part of the nanospheres after being contacted by the same homogeneity among the monomers, so that the excessive crosslinking among the nanoparticles is reduced as much as possible.
Observe the IR spectrum (FIG. 2) at 715cm-1A new stretching vibration peak appears, which is derived from the polysubstitution reaction on the benzene ring and is positioned at 651cm-1A new absorption peak is also appeared, which comes from C-Cl vibration, 1436cm-1、1505cm-1The absorption peak intensity of the carbon-carbon double bond of the benzene ring is further improved, and the benzene ring hydrogen is substituted in the reaction process. 2930cm-1The absorption peak is the vibration of C-H in methylene, which proves that the hypercrosslinking reaction forms methylene cross-linking bridge, which proves that in FeCl3Under the catalytic action of (A), R-SiO2The chloromethyl on @ DCX reacts on reactive benzene ring to form methylene cross-linking bridge between template and reaction monomer in the reaction process to form polymer network, which proves the existence of hypercrosslinking reaction, namely R-SiO2@ xCX.
3.2 Effect of hypercrosslinking reaction conditions on HPP
3.2.1 Effect of catalyst concentration on HPP
The shape and structure of the crosslinking reaction product are often influenced by the dosage of the catalyst, and in order to explore the influence of the dosage of the catalyst on the hypercrosslinking reaction, three different dosages of the catalyst, namely 1.1g, 1.6g and 2g, are adopted in the experiment.
Observe the nitrogen adsorption and desorption curves (FIG. 3(a)) for three different catalyst dosages, the adsorption amount of the rapid increase in the low-pressure region, the hysteresis hole of the medium-pressure region and the adsorption amount increase table of the high-pressure regionThe sample is shown to have a micropore structure, a mesopore structure and a macropore structure, and the HPP prepared by combining the DFT pore size distribution curve in FIG. 3(b) is known to belong to hierarchical pore materials with three-dimensional layered structures. As can be seen from Table 1, the specific surface area of the sample increased from 562m when the catalyst concentration was increased from 1.1g to 1.6g2·g-1Increased to 889m2·g-1The micropore area is also from 265m2·g-1Is greatly lifted to 567m2·g-1. The total pore volume also increases with the increase of the dosage, wherein, the pore volume of the micropores is increased by 0.12cm3·g-1The growth is 0.23cm3·g-1The catalyst occupies a larger proportion of the change of the total pore volume, which shows that the crosslinking degree of the reaction is deepened along with the increase of the concentration of the catalyst, and the number of micropores is increased along with the increase of the concentration of the catalyst. When the catalyst concentration is increased to 2g, the specific surface area is reduced to 634m2·g-1However, the micropore volume remained essentially unchanged, indicating that the degree of crosslinking of the polymer was not affected to the same extent by the catalyst concentration. Referring to FIG. 3(b), the micropore distribution ratio of the sample at 2g was decreased, which indicates that when the catalyst exceeds a certain range, the degree of crosslinking is rather limited, thereby affecting the amount of micropores formed.
TABLE 1 pore Structure parameters for different catalyst concentrations HPP
3.2.2 Effect of hypercrosslinking temperature on HPP
In order to explore the influence of the hypercrosslinking temperature on the morphology structure of HPP, a feasible way for accurately regulating and controlling the nanostructure of the sample is found. The experiment adopts a series of reaction temperatures of 30 ℃, 50 ℃, 70 ℃, 80 ℃ and 90 ℃ to carry out the hypercrosslinking polymerization reaction.
As can be seen from fig. 4, when the cross-linking temperature is increased from 30 ℃ to 90 ℃, the morphology of the sample does not change greatly, the nanospheres are hollow, and the three-dimensional network structure with spheres stacked on each other is maintained as a whole. When the hypercrosslinking temperature is 30 ℃, the interior of the sample is a regular cavity, and the coating layer is semitransparent, which indicates that the hypercrosslinking reaction forms a crosslinked framework on the surface of the silicon sphere. When the temperature is increased to 50 ℃, the shell thickness of the sample surface is reduced, two or three small holes are formed at the intersection of the nanometer spherical shells, which indicates that when the Friedel-crafts reaction occurs, the nanometer spheres are tightly attached together, the surface polymerization part covers the sphere to form an external shell, and after the silicon spheres are removed, the intersection of the shells forms a channel to connect adjacent cavities. When the hypercrosslinking temperature is further increased to 70 ℃, uneven rough layered materials appear on the surfaces of the nanospheres, a small amount of bonding occurs among the particles, and the collapse phenomenon appears on partial shell layers, so that the formed cross-linked shell layers do not reach the optimal strength, which shows that the hypercrosslinking reaction at the wall thickness is still in progress. Meanwhile, the figure clearly shows that at different hypercrosslinking temperatures, the single sphere can form a whole with uniformly distributed pores through the cross-linking bridges among the spheres, and all cavities are in a stacked structure connected with each other. However, when the super-crosslinking temperature reaches 90 ℃, the crosslinking phenomenon occurs among the hollow spheres.
And carrying out thermogravimetric analysis by selecting HPP before removing the silicon spheres so as to analyze the grafting condition of the nanospheres at different temperatures. As can be seen from fig. 5, the weight loss ratios at different crosslinking temperatures were all different, and it was found that the graft ratio could be changed by the change in the crosslinking temperature. When the temperature is 80 ℃, the weight loss rate of the sample reaches 91.1 percent, which is far higher than the weight loss at other temperatures, and the change of the crosslinking temperature can influence the super-crosslinking polymerization reaction on the surface of the nanosphere.
It can be seen from table 2 that the difference of the crosslinking temperature affects the distribution of hierarchical pores, and the larger the crosslinking temperature is, the larger the specific surface area and the micropore area are. When the reaction temperature is 30 ℃, the hypercrosslinking reaction can still smoothly occur, the formed cross-linking bridge forms micropores, and the whole structure still maintains the hierarchical pore structure. As is clear from Table 2, the specific surface area of the sample at this time was 535m2·g-1The micropore area is 267m2·g-1， The area of the micropores accounts for nearly 50% of the total specific surface area, and the pore volume of the micropores is 0.1cm3·g-1Much lower than 0.46cm3·g-1And then a series of temperature conditions substantially similar to this, illustrate that the microporous structure is capable of providing a specific surface area far in excess of that provided by the external pores. When the temperature is raised to 50 ℃, the specific surface area is raised to 597m2·g-1The micropore area is 270m2·g-1The micropore area is only slightly increased to 284m until the temperature is 70 DEG C2·g-1And the external pore area is from 268m at 30 DEG C2g-1To 385m at 70 DEG C2·g-1The change in pore size indicates that the hypercrosslinking reaction proceeds slowly from 30 ℃ to 70 ℃ since the degree of crosslinking affects the area of the microporous structure. Since the mesopores and macropores mainly originate from the stacking among the nanoparticles, the increase of the external pore volume indicates that the hypercrosslinking reaction still proceeds on the surface of the nanospheres.
When the crosslinking temperature reaches 80 ℃, the specific surface area is increased to 889m2·g-1The area of the micropores is increased to 567m2·g-1Simultaneously, the pore volume of the micropores is increased to 0.23cm3·g-1The area of the micropores represents 63% of the total area, and the specific surface area of the sample is considerably increased compared to 70 ℃, as can also be seen from the pore size distribution curve. The increase of the micropore area means that the crosslinking rate of the reaction is greatly increased, the combination of methylene bridges among molecules is more and more compact, the original gap is gradually filled with the crosslinking bridge between the benzene ring and the outer layer of the benzene ring, and the reduction of the external specific surface area also proves that the method has the advantages of high reaction efficiency, high reaction efficiency and low cost. When the reaction temperature is 90 ℃, the specific surface area and the micropore volume of the catalyst respectively have a trend of decreasing and are 791m2·g-1And 0.18cm3·g-1The total pore volume is even lower than that of the sample at 70 ℃, so that the factor for controlling the total pore volume is mainly the microporous structure, the number of micropores is large, the micropore volume is increased along with the increase of the total pore volume, and the total specific surface area can be improved. At this time, the hypercrosslinking temperature does not increase the crosslinking degree between the nanospheres any more, and the number of micropores does not increase any more.
TABLE 2 HPP pore structure parameters at different hypercrosslinking temperatures
3.2.3 Effect of hypercrosslinking time on HPP
As can be seen from Table 3, as the hypercrosslinking time is extended, the specific surface area and the micropore volume of the sample are increased. When the crosslinking time is 3h, the specific surface area is 386m2·g-1The pore volume of the micropores is 0.04cm3·g-1The reaction does not proceed completely due to the short crosslinking time, at which point the external pore volume occupies a substantial portion of the total pore volume. With the increase of the crosslinking time, the specific surface area and the pore volume of the micropores slowly rise until the specific surface area is extended to 18h and is 450m2·g-1The specific surface area of the micropores was 229m2·g-1And the pore volume of the micropores is close to that of the outside pores, which indicates that the crosslinking reaction between the spheres is continuously proceeding and the formation of the crosslinking bridges leads to the increase of the area ratio of the micropores.
When the crosslinking time is increased from 18h to 24h, the total pore volume is increased from 0.42cm3·g-1Rise to 0.88cm3· g-1At the same time, the specific surface area is greatly increased from 450m2·g-1Rises to 889m2·g-1Almost doubled in comparison to the surface area. When the crosslinking time exceeds 18h, the micropore volume of the sample is greatly improved from 0.09cm in 18h3·g-1Rise to 0.23cm of 24h3·g-1This indicates that the extended hypercrosslinking time contributes to the progress of the Friedel-crafts reaction and that the degree of crosslinking rises rapidly after a certain time. After careful comparison, the increase of the specific surface area almost entirely results from the increase of the number of micropores, and since the micropore structure in the sample mainly comes from the self-crosslinking reaction of benzyl groups among benzene rings, the higher the degree of crosslinking among spheres is, the denser the crosslinking bridge structure is, and the more micropores are formed. At this time, the degree of crosslinking reaches the highest level, and the increase of the external specific surface area is far less than thatThe increase in the number of micropores is likely because the individual nanoparticle particles form a bridging moiety containing a large number of micropores through a crosslinking reaction, and the increase in the total specific surface area is benefited by the large increase in the area of the micropores. In combination with the above trend of pore volume change, the hypercrosslinking reaction time influences the progress of the crosslinking reaction, and after more than 18h, the crosslinking degree can be further improved, and the maximum crosslinking degree is achieved at 24 h.
TABLE 3 pore Structure parameters for different hypercrosslinking times HPPs
The experiment results are combined, and the catalyst concentration, the reaction temperature and the reaction time can all influence the hypercrosslinking reaction, so that the pore structure of the HPP is influenced. Increasing or decreasing the catalyst concentration both reduces the specific surface area of the hypercrosslinked product; when the hypercrosslinking temperature is increased from 30 ℃ to 90 ℃, the crosslinking degree of the product is gradually increased, the specific surface area is higher, and the maximum value of 889m is reached when the specific surface area is 80 DEG2·g-1At this time, the surface area of the micropores also reaches a maximum value of 567m2·g-1The result shows that the micropore structure in the product can be effectively increased by increasing the temperature, and the specific surface area of the product is further increased; when the hypercrosslinking time was gradually increased from 3h to 18h, the specific surface area increased slowly, while when the crosslinking time reached 24h, the specific surface area increased significantly, indicating that too low a hypercrosslinking time easily resulted in incomplete crosslinking reaction. Finally obtaining the optimal hyper-reaction condition for preparing the hierarchical porous polymer HPP by the reactive template agent: when the catalyst dosage is 1.6g, the crosslinking temperature is 80 ℃, and the crosslinking time is 24 hours, the specific surface area of the HPP reaches the maximum value of 899m2·g-1。
3.3 Effect of carbonation conditions on HPC
3.3.1 Effect of carbonization temperature on HPC
From Table 4, it can be found that when the carbonization temperature is raised from 700 ℃ to 1000 ℃, the specific surface area of the sample is from 736m2·g-1Increase to 2388m2·g-1At the same time, the area of the micro-holesThe micropore area is increased along with the increase of the carbonization temperature, and is 414m from 700 ℃ to 1000 DEG C2·g-1、824m2·g-1、1522m2· g-1And 1892m2·g-1It can be seen that in a certain range, the higher the carbonization temperature is, the larger the specific surface area is, and the larger the micropore area is. Because the sample HPP forms a three-dimensional network by means of the cross-linking bridges among the nanospheres, molecules in the cross-linking bridges shrink probably due to a high-temperature environment, a plurality of micropore structures are generated, and the specific surface area is increased accordingly.
As can be seen from fig. 4, the specific surface area ratios of the micropores of the samples at different temperatures all exceeded 50%, and the specific surface areas of the micropores almost reached 80% in the total specific surface area when the carbonization temperature exceeded 800 ℃, further indicating that the specific surface areas of the micropores are the main specific portion of the total specific surface area. Wherein, at 700 ℃, the specific surface area ratio of the micropores is only 56%, after the temperature rises to 900 ℃, the specific surface area ratio of the micropores is 81% at the maximum ratio, and when the temperature further rises to 1000 ℃, the specific surface area ratio of the micropores slightly decreases, which indicates that the carbonization temperature has a large influence on the micropore structure in the sample.
Table 4 pore structure data for different carbonization temperatures HPC
As is clear from Table 4, the total specific surface area was 736m at a carbonization temperature of 700 ℃2·g-1Wherein the specific surface area of the micropores accounts for 56%, and the total pore volume and the pore volume of the micropores are respectively 0.88cm3·g-1And 0.17cm3·g-1. Compared with HPP, the micropore volume is reduced from 0.23cm3·g-1Reduced to 0.17cm3·g-1Corresponding pore area from 517m2·g-1Down to 414m2·g-1But the total pore volume and the external specific surface area remain unchanged.
When the temperature was raised to 800 ℃, the total specific surface area increased to 1030m2·g-1At this time, the total pore volume was 0.89cm3·g-1Almost constant, but the pore volume of the micropores is from 0.17cm3·g-1Increased to 0.32cm3·g-1The specific surface area of the micropores is also from 414m2·g-1Rise to 814m2·g-1. Under the condition of keeping the total pore volume unchanged, the external pore volume is from 0.71cm3·g-1Down to 0.51cm3·g-1The decreasing fraction is slightly more than the increasing fraction of the pore volume of the micropores, and it is suspected that at this time as the temperature increases, part of the cross-linking bridges start to generate micropores, and further shrinkage causes some of the mesopores to gradually transform into the micropore fraction.
When the temperature is increased to 900 ℃, the total specific surface area is increased to 1868m2·g-1The area of the micropores is increased to 1522m2·g-1The pore volume of the micropores and the total pore volume are respectively increased to 0.96cm3·g-1And 1.57cm3·g-1. In the process, the area of the micropores and the area of the mesopores are simultaneously and greatly increased, the increase rate of the area of the micropores is about 84 percent, and the increase rate of the area of the mesopores and the macropores is about 67 percent. Indicating that the number of macropores increases with the increase in the number of micropores.
When the temperature is raised to 1000 ℃, the total specific surface area is from 1868m2·g-1Increased to 2388m2·g-1The micro-hole area is from 1868m2·g-1Increased to 1892m2·g-1External pore volume from 0.96cm3·g-1Increased to 1.21cm3· g-1. At this time, the area of the micropores and the total pore volume are still increasing, but the corresponding growth rate tends to decrease compared with the change from 800 ℃ to 900 ℃. The volume of the medium and large pore region reaches a peak value, the rigidity of the whole framework determines the structural stability of the sample, and the collapse phenomenon is not found in appearance, so that the internal pores are possibly separated from each other.
3.3.2 Effect of carbonation time on HPC
In addition to the carbonization temperature, the carbonization time is also an important factor affecting the carbonization process. Three carbonization times of 1h, 3h and 10h were used in the experiment to study the effect level of the carbonization time on different pore structures of HPC.
As can be seen from Table 5, when the carbonization time was extended from 3h to 10h, the specific surface areas of the respective samples were from 1868m2·g-1Increase to 2221m2·g-1. Meanwhile, the carbonization yield is 26%, 34% and 26% in sequence, the carbonization yield reaches the highest point at 6h, and the carbonization yield is the same at 3h and 10h, which may be that the total specific surface area is increased along with the carbonization time, but the contribution degree of different areas in the hierarchical pore structure to the total specific surface area is different. Probably, the phenomenon of shrinkage and even collapse of the hypercrosslinked skeleton occurs due to the extension of the carbonization time, and the reduction rate of the number of mesopores and macropores is lower than the increase rate of the number of micropores at 6 h. At time 10h, a portion of the previously generated meso-macropores was converted into micropores, at which time the external specific surface area was from 331m2·g-1Increase to 505m2·g-1It indicates that the micropores are not increased greatly any more and the skeleton is shrunk greatly.
TABLE 5 pore structure data for different carbonization temperatures HPC
As can be seen from Table 6, the micropore volume was 0.64cm when the carbonization time was 6 hours3·g-1(ii) a When the time is prolonged to 10h, the pore volume of the micropores is increased to 0.69cm3·g-1The growth amount is only 0.05cm3·g-1This indicates that the carbon skeleton of HPC has already reached a steady state and smaller molecules no longer escape to form micropores. The overall specific surface area of HPC increased with increasing carbonization time, indicating that carbonization time favors the formation of micropores, the micropore area being the major portion of the total specific surface area. The above results show that HPC maintains a stable structure over different carbonization times, and also indicate hypercrosslinkingThe skeleton can be well inherited in the carbonization process.
TABLE 6 pore structure data for different carbonization times HPC
3.3.3 Effect of carbonization ramp Rate on HPC
Under the condition of fixing the carbonization temperature and the carbonization time, the change of the carbonization temperature rise rate generally has a plurality of influences on the structure of the carbon material, and in order to find the action factors of the carbonization temperature rise rate on each structure in the HPC hierarchical hole, three temperature rise rates of 2 ℃/min, 5 ℃/min and 10 ℃/min are adopted in the experiment.
As shown in Table 7, the HPC total specific surface area was from 889m when the carbonization ramp rate was 2 ℃/min, compared to HPP2·g-1Increased to 1079m2·g-1Micro-pore area from 567m2·g-1Increased to 803m2·g-1But an external pore volume of from 0.65cm3·g-1Down to 0.60cm3·g-1It is indicated that the skeleton shrinks slightly during carbonization. When the heating rate is 5 ℃/min, the total specific surface area is further increased to 1868m2· g-1Pore volume of the micropores is from 0.32cm3·g-1Increased to 0.61cm3·g-1External pore volume is increased to 0.96cm3· g-1. For a sample, the increase of the micropore area means that the occupation ratio of a micropore structure is increased, which obviously increases the specific surface area of the carbon material, and the fact that the higher the carbonization temperature rise rate is in a certain range, the larger the specific surface area of the sample is, the pore volumes of micropores, mesopores and macropores are increased, which is probably because the skeleton is always shrunk, so that the number of the mesopores and the macropores is increased, and a plurality of small molecules are escaped to form micropores. However, when the heating rate reaches 10 ℃/min, the external pore volume and the micro-scaleThe hole capacities of the holes all slide down sharply and respectively go from 0.96cm3·g-1And 0.61cm3·g-1Down to 0.25cm3·g-1And 0.25cm3· g-1It is shown that the carbonization temperature rise rate is too high, resulting in a large amount of collapse inside the sample and a part of the micropores turning into macropores.
TABLE 7 pore Structure data for different carbonization heating Rate HPC
The results of the above experiments show that different carbonization conditions have different effects on the specific surface area of HPC, and the total specific surface area of HPC can be effectively changed by the carbonization time, the carbonization temperature and the carbonization temperature rise rate. When the carbonization temperature is increased from 700 ℃ to 1000 ℃, the total specific surface area of HPC is from 736m2·g-1Is lifted to 2388m2·g-1Wherein the micropore area is from 414m2·g-1Increased to 1892m2·g-1The microporous structure is an important factor for greatly increasing the total specific surface area of HPC. When the carbonization time is from 3h to 10h, the total specific surface area is from 1868m2·g-1Rises to 2221m2·g-1The micropore area is from 1522m2·g-1Rises to 1716m2· g-1It is shown that a suitable extension of the carbonization time is advantageous for increasing the HPC specific surface area. While the carbonization temperature rise rate is increased from 2 ℃/min to 10 ℃/min, the total specific surface area shows the trend of rising firstly and then falling, and finally, the total specific surface area is from 1079m2·g-1Down to 842m2·g-1This means that increasing the carbonization temperature increase rate is beneficial to the improvement of the HPC specific surface area to some extent, however, an excessively high temperature increase rate may cause collapse of the carbon material structure, thereby reducing the HPC total specific surface area. Therefore, through comparative experiments under different carbonization conditions, the optimal carbonization conditions for preparing the hierarchical porous material HPC are that the carbonization temperature is 1000 ℃, the carbonization time is 3h, the carbonization temperature rise rate is 5 ℃/min, and the specific surface area of the HPC reaches the maximum value 2388m2·g-1。
3.4 study of adsorption Properties
3.4.1 Effect of the amount of HPC used on its adsorption of methylene blue
To investigate the effect of HPC usage on its adsorption of methylene blue, the Applicant chose 10mL of MB standard solution with a concentration of 50mg/L and placed it in an Erlenmeyer flask, weighed 2mg, 4mg, 6mg, 8mg and 10mg of HPC separately and added it to the above standard solution, stirred magnetically at room temperature 25 ℃ and a stirring speed of 250rpm until the adsorption equilibrium, and observed the adsorption equilibrium process.
Fig. 6 shows the effect of HPC dosage on methylene blue adsorption, and as shown in fig. 6, when HPC dosage is increased from 2mg to 10mg, the adsorption rate of HPC on methylene blue tends to increase and decrease. When the amount of the addition was 2mg, the adsorption rate reached 98%, and when the amount of the addition was increased to 6mg, the adsorption rate reached the maximum value of 100%. When the adding amount is further increased from 8mg to 10mg, the adsorption rate is reduced from 98.8% to 97.9%. As can be seen from fig. 6(b), the adsorption amount decreased as the amount of the sample added increased. It may be that when the amount of the sample is small, the binding sites with methylene blue inside the sample are not sufficient, and thus the adsorption rate tends to increase as the amount is increased. When the adding amount of the sample is increased, the concentration of methylene blue is kept unchanged, the adsorption sites of the sample are occupied by gradually changed methylene blue molecules, the adsorption rate of the sample per unit mass is reduced, and the adsorption amount is reduced accordingly.
3.4.2 Effect of solution pH on HPC adsorption of methylene blue
To explore the adsorption of HPC to methylene blue at different pH values, an initial standard solution was selected with pH values set at 1.63, 3.08, 6.44, 9.39, 11.44 until adsorption equilibrium.
As shown in FIG. 7, the pH of the solution was set in the range of 1 to 13. When the pH value is 1.63-6.44, the adsorption rate is increased from 42.9% to 94.7%, and the trend is gradually increased. At pH 9.39, HPC achieved maximum adsorption performance at this point, with an adsorption rate of 99.7%. As the pH further increased to 11.44, the adsorption rate dropped to 80.4%. Probably because of H in the solution under acidic or strongly acidic conditions+With a high number of ions occupying the HPC surface of the carbon materialBinding sites, such that adsorption of methylene blue is inhibited. With the increase of pH, the vacancy of the adsorption site is beneficial to further adsorption under the alkaline condition. However, when the pH is too high, OH in the solution-Excessive concentration of the surfactant can inhibit the electronegativity of the HPC surface, thereby being unfavorable for H+The adsorption rate is reduced due to the adsorption of ions. From the above, the adsorption capacity of HPC to methylene blue can be effectively controlled by changing the pH.
3.4.3 Effect of adsorption time on HPC adsorption of methylene blue
In order to explore the adsorption of HPC on methylene blue under different adsorption times, an initial standard solution is selected for an experiment, and the adsorption sampling time is set to be 2.5min, 5min, 10min, 20min, 30min, 50min, 60min, 75min and 90min until the adsorption is balanced.
As shown in fig. 8(a), the longer the adsorption time, the higher the adsorption rate of HPC to MB. HPC is able to adsorb methylene blue completely over a time range. The adsorption rate is rapidly increased within 5min before adsorption, the adsorption rate reaches 59% when 5min is carried out, the adsorption rate is increased from 64% to 99% from 10min to 60min, the adsorption rate is gradually reduced until 60min later, the adsorption rate is not increased any more, and the adsorption reaches the balance. As can be seen from comparison of FIG. 8(b), the amount of methylene blue adsorbed by the sample was at equilibrium.
Because HPC contains a large amount of porous structures and can provide a plurality of adsorption sites for adsorbing methylene blue, the rate is extremely high in the initial stage of adsorption, and the high concentration of methylene blue solution causes molecular motion active jump, thereby promoting the adsorption of the methylene blue by the HPC. When the adsorption time is prolonged continuously, adsorption sites inside HPC are filled and occupied by methylene blue molecules, the adsorption rate is further reduced gradually, the reaction equilibrium time is delayed, and complete adsorption is not carried out until one hour is reached.
3.4.4 Effect of adsorption temperature on HPC adsorption of methylene blue
In order to investigate the adsorption effect of HPC on methylene blue at different temperatures, an initial standard solution was selected, and the adsorption temperatures were 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃ respectively until adsorption equilibrium was reached.
As can be seen from FIG. 9, the adsorption temperature is increased from 25 ℃ to 40 ℃, the adsorption rate is gradually increased, the maximum adsorption rate is reached at about 40 ℃, and then the temperature is continuously increased, and the adsorption rate is slightly decreased, which indicates that the adsorption reaction belongs to physical adsorption. Within a certain temperature range, the temperature rise is beneficial to the adsorption process because the temperature raises the activity of methylene blue molecules, increases the movement rate of the methylene blue molecules, and accelerates the adsorption process, which indicates that the process of HPC adsorbing the methylene blue is an endothermic reaction.
In conclusion, the dye molecules in the solution can be effectively adsorbed by using HPC as the adsorbent. The dosage, pH value, adsorption temperature and adsorption time of the adsorbent all affect the adsorption process, the adsorption condition is optimized, and the adsorption rate can reach more than 95%; the adsorption process conforms to a pseudo-second-order kinetic model and a particle internal diffusion model, and shows that the adsorption reaction simultaneously comprises chemical adsorption and micropore internal adsorption.
3.5 electrochemical Properties
HPC has the potential to be an electrode material for making supercapacitors, since it contains abundant micropores, provides a high specific surface area, and channels connect various parts of the internal structure. The zinc ion hybrid super capacitor integrates the advantages of a high-energy zinc ion battery and a high-power super capacitor, and has become one of the development trends of energy storage equipment in recent years. The experiment combines electrochemical characteristics such as mass specific capacitance, coulombic efficiency and circulation stability, and discusses the application of HPC in the field of zinc ion hybrid supercapacitors.
As can be seen from the cycle characteristics curve of FIG. 10(a), the discharge capacity was 58mAh · g when the coulombic efficiency was taken as a maximum of 100%, and the coulombic efficiency had reached 88% during the second charge and discharge-1The discharge capacity hardly changes any more with the gradual increase of the cycle number, and is kept stable all the time. After the number of cycles reached 100 times, the discharge capacity was still consistent with the capacity at the time of the initial cycle, which indicates that the electrode material had excellent cycle stability. From the rate characteristic curve of FIG. 10(b), when the current density was 0.1A · g-1The increase of the cycle number increases the capacitance, and the mostThe height reaches 35 mAh.g-1At different current densities, the reversible capacity also changes with increasing current density. When the current density is reduced to 0.1A · g again-1After 150 cycles, the reversible capacity is increased and kept stable, reaching 40mAh g-1Again, the excellent stability of the capacitor capacity is demonstrated.
Fig. 11(a) and 11(b) show the charging and discharging curves and ac impedance test of the HPC carbon material electrode in the first three rounds, respectively. When the current density is 0.1A · g-1As the voltage increases, the capacitor capacity also increases. In the first three circles of charge and discharge processes, the curve coincidence degree of the 3 rd circle and the 2 nd circle is good, and the electrode material has good cycle stability. According to the impedance test result, as seen from fig. 11(b), the impedance curve is composed of a straight line of the low frequency region and a circular arc curve of the high frequency region, the low frequency region has a diagonal inclination angle larger than 45 degrees, which indicates that the low frequency region has a smaller resistance, and the diameter size of the high frequency region semi-circular curve indicates that the resistance value of the electrode material is smaller, which is beneficial to charge transfer and has good conductivity.
In conclusion, the electrode material of the zinc ion hybrid supercapacitor is prepared by using HPC. After 100 times of circulation, the circulation discharge capacity is stabilized at 60mAh g-1About when the current density is 0.1A · g-1The capacitance increases with the increase of the cycle number, and can reach 35mAh g at most-1After 150 cycles, the reversible capacity can reach 40 mAh.g-1. The charging and discharging curves and the impedance curves of the first three circles show the stability of the electrode material.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (6)
1. A method for preparing a hierarchical porous carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1)R-SiO2preparation of
Mixing SiO20.5g of dry tetrahydrofuran THF (20 ml) and 1.5g of trichloro [4- (chloromethyl) phenyl ] are added]A mixture of silanes; in N2In the atmosphere, 5.0ml of dry THF and 1.2ml of triethylamine are uniformly mixed, added into the system at a constant speed for reaction for 8 hours, and then reacted in the air for 18 hours; after the reaction was complete, the product was washed with EtOH and THF at least 3 times and dried;
(2)R-SiO2preparation of @ DCX
In N2In the atmosphere, adding R-SiO20.5g of FeCl was uniformly dispersed in 10ml of dichloroethane DCE and dried3-1.1-2.0g of the mixture is quickly added into the mixture and evenly stirred, 1.5g of p-dichlorobenzene DCX is dissolved in 10ml of dichloroethane DCE, the mixed solution is added into a three-neck flask when the reaction system is heated to 70-90 ℃, and the mixed solution is dropwise added for 6 hours and kept reacting for 18 hours; washing the product with deionized water, washing with deionized water and methanol to colorless, washing with diethyl ether for 3 times, and drying;
(3) preparation of HPP and HPC
Preparing 10% HF, mixing R-SiO2Adding @ DCX into the mixture, keeping magnetic stirring at 500rpm for 24h, washing off residual HF solution, drying at 60 deg.C for 12h to obtain hierarchical porous polymer HPP, placing HPP, N in a tube furnace2The purging speed is 80-100ml/min, the carbonization temperature is 700-.
2. The method for preparing a hierarchical porous carbon material according to claim 1, wherein: catalyst FeCl in step (2)3The amount used was 1.6g and the crosslinking temperature was 80 ℃.
3. The method for preparing a hierarchical porous carbon material according to claim 1, wherein: the carbonization temperature in the step (3) is 1000 ℃, the carbonization temperature rise rate is 5 ℃/min, and the carbonization time is 3 h.
4. The hierarchical porous carbon material produced by the production method according to any one of claims 1 to 3.
5. Use of the hierarchical porous carbon material of claim 4 in the preparation of dye adsorbents or electrode materials.
6. Use according to claim 5, characterized in that: when the hierarchical porous carbon material is used as a dye adsorbent, 10mL of MB solution with the concentration of 50mg/L is used as standard solution, the dosage of HPC is selected to be 6mg, and the mixture is stirred and adsorbed under the conditions that the pH value is 9.39, the adsorption sampling time is 60min, and the adsorption temperature is 40 ℃.
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